CN103938043B - High-phosphorus manganese produces pure manganese silumin technique - Google Patents
High-phosphorus manganese produces pure manganese silumin technique Download PDFInfo
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Abstract
The invention discloses a kind of high-phosphorus manganese and produce pure manganese silumin technique, comprise the following steps: high-phosphorus manganese, coke, silica drop in mineral hot furnace by (1), obtain manganese-silicon; (2) will fill in the intermediate frequency furnace of industrial silicon tankage, decarburization flux and a small amount of insulating covering agent in the manganese-silicon impouring obtained in step (1); (3) by the stirring bag of the in-built silicocalcium of manganese-silicon impouring that obtains in step (2) or Si-Ba alloy, a small amount of slag former; (4) by part high silicon manganese-silicon alloy and Australia ore deposit, lime and fluorite impouring electric arc furnace, Mn-rich slag is obtained; (5) high silicon manganese-silicon alloy in Mn-rich slag step (4) obtained and step (3) reacts; (6) alloy impouring step (5) obtained, built with in the intermediate frequency furnace of aluminium scrap or aluminium ingot, obtains manganese silumin.The present invention adopts above-mentioned technique, manganese silumin can be made to conform to current standards requirement, avoid product efflorescence, and cost is lower simultaneously.
Description
Technical field
The present invention relates to alloy smelting field, be specifically related to a kind of high-phosphorus manganese and produce pure manganese silumin technique.
Background technology
Last century five, the sixties, USSR (Union of Soviet Socialist Republics) metallargist finds that manganese sial composite alloy has degree of depth deoxidation and can promote the feature of steel mechanical property in steel-making, organize huge team to research and develop this product for this reason, they have formulated two sets of plan: aluminium is dissolved in high-Si aluminum cast or manganese-silicon melt by the first, its two be with carbon reduce in mineral hot furnace containing manganese, silicon, aluminium furnace charge produce manganese silumin, but smelt products obtained therefrom because of phosphorous, carbon is higher, very easily efflorescence, makes product cannot use in steelmaking process.Domestic from last century the nineties, You Duojia manufacturing enterprise in intermediate frequency furnace by after manganese-silicon or scrap melting, add electrolytic manganese again, aluminium ingot carries out tune and convert and produce manganese silumin, Here it is is called the production technique of fusion process, and the shortcoming of this technique is that production cost is high.
In addition, as everyone knows, China's manganese resource is three high and one low (iron is high, phosphorus is high, silicon-dioxide is high, manganese low), and this brings great difficulty to smelting manganese-series ferroalloy.High-phosphorus manganese is comparatively large at the reserves of China, but exceedes GB 2 ~ 4 times with phosphorus content in the manganese-silicon of high-phosphorus manganese production, and does not also have a set of rational technique to be used to high-phosphorus manganese at present.
Summary of the invention
A kind of high-phosphorus manganese is the object of the present invention is to provide to produce the method for manganese silumin, solve conventional carbon hot reducing method, fusion process produce manganese silumin do not reach current standards requirement, product is efflorescence very easily, cause to use in STEELMAKING PRODUCTION, cost is higher simultaneously, and downstream user is difficult to the problem accepted.
The present invention for achieving the above object, realizes: high-phosphorus manganese produces pure manganese silumin technique, comprises the following steps by the following technical solutions:
(1) high-phosphorus manganese, coke, silica are dropped in mineral hot furnace, obtain high phosphorus manganese-silicon, the mass percent of its each component is as follows: Mn:65 ~ 73%; Si:16 ~ 18%; P:0.6 ~ 1.2%; C:1.5 ~ 2.0%; S:0.03 ~ 0.04%, all the other are Fe;
(2) by filling in the high phosphorus manganese-silicon impouring obtained in step (1) in the intermediate frequency furnace of industrial silicon tankage, decarburization flux and a small amount of insulating covering agent, the silicon content of high phosphorus manganese-silicon being promoted to more than 25%, treating load melting complete, skim, come out of the stove;
(3) by the stirring bag of the in-built silicocalcium of high phosphorus manganese-silicon impouring that obtains in step (2) or Si-Ba alloy, a small amount of slag former, agitation as appropriate, obtains high silicon manganese-silicon alloy, and in the high silicon manganese-silicon alloy of now output, phosphorus content is not higher than 0.15%;
(4) high silicon manganese-silicon alloy obtained in step (3) is got 20%, impouring is equipped with in the electric arc furnace of Australia ore deposit, lime and fluorite, treat load melting completely can to come out of the stove, obtain carbon content not higher than 0.1% micro-carbon ferromanganese and Fe content be 25% ~ 30%, basicity is the Mn-rich slag of 1.8 ~ 2.2;
(5) Mn-rich slag step (4) obtained and remaining high silicon manganese-silicon alloy stir wrap in carry out desiliconization, dephosphorization and increase manganese reacting, in alloy silicon content not higher than 10% time and stopped reaction;
(6) be equipped with in the intermediate frequency furnace of aluminium scrap or aluminium ingot by the alloy impouring that step (5) obtains, cold melt aluminium scrap or aluminium ingot under the covering of insulating covering agent, obtain manganese silumin, and the mass percent of its each component is as follows:
Mn：70~80%；Si：5~10%；Al：4~10%；P<0.1%;C<0.1%; S：0.03~0.04%。
Further, in described step (5), Mn-rich slag and high silicon manganese-silicon alloy react except obtaining silicone content not higher than except the alloy of 10%, also obtain waste residue, carry out shrend to this waste residue, obtain the raw material that can be used for manufacturing cement.
Further, the high silicon manganese-silicon alloy that described step (3) obtains can directly be poured in mold, obtains high-Si aluminum cast product.
Further, micro-carbon ferromanganese that described step (4) obtains can directly be poured in mold, obtains micro-carbon ferromanganese product.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the invention solves a difficult problem for manganese-silicon phosphorus deep removal, carbon drop, phosphorus content in manganese silumin is down to minimum, accomplish controlled to the content of manganese, silicon, aluminium, carbon simultaneously, make the not easily efflorescence in smelting process of manganese silumin, the production not being only pure manganese silumin opens an approach, and has expanded scope for the reasonable employment of reserves high-phosphorus manganese larger, distributed more widely.
(2) the present invention the different demands to product can adjust according to the difference of phosphorus content in manganese ore and user, micro-carbon-manganese alloy, high silicon manganese-silicon alloy, manganese silumin can be obtained, thus meet the different needs, simultaneously, raw material is changed into product as much as possible, achieves effective utilization of resource.
(3) a lot of raw material of the present invention is waste product or the tankage of every profession and trade recovery, as aluminium scrap, industrial silicon tankage etc., not only effectively reduces cost, also a saving limited resources, make it recycle.
(4) operation that the present invention adopts all is carried out under low temperature, closed state, both the oxidation loss of the elements such as manganese, silicon, aluminium, barium, calcium had been reduced, reduce again or even avoid the generation of flue gas, thus reduce the input of off gas treatment, discharge, also relatively little on the impact of environment.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1:
A kind of high-phosphorus manganese described in the present embodiment produces pure manganese silumin technique, comprises the following steps:
Step (1), high-phosphorus manganese, coke, silica are dropped in mineral hot furnace, obtain liquid high phosphorus manganese-silicon, the mass percent of its each component is: Mn:70%; Si:17%; P:0.6%; C:1.5%; S:0.03%, all the other are Fe;
Step (2), get this liquid high phosphorus manganese-silicon 3000Kg in step (1), and will fill in the intermediate frequency furnace of industrial silicon tankage (siliceous 75%), decarburization flux and a small amount of insulating covering agent in its impouring, treat load melting complete, skim, come out of the stove, now in manganese-silicon, the mass percent of each component is Mn:62%; Si:25%; P:0.35%; C:0.3%; S:0.03%;
Step (3), the in-built silicocalcium of the manganese-silicon impouring (silicon: 55% will obtained in step (2), 28%) or Si-Ba alloy (silicon: 40% calcium:, barium: in the stirring bag of 25%) (note: be mass percent), a small amount of slag former, agitation as appropriate, now the high silicon manganese-silicon alloy phosphorus content of output is 0.15%;
Step (4), the high silicon manganese-silicon alloy that step (3) obtains is got 20%, impouring is equipped with in the electric arc furnace of Australia ore deposit, lime and fluorite, Australia ore deposit is mainly containing the Mn of about the 42% and Fe of about 8%, lime is then common lime raw material, containing the calcium oxide of about 85%, treat load melting completely can to come out of the stove, obtain micro-carbon ferromanganese, the mass percent of its each component is: Mn:80%; Si:0.8%; C:0.1%, also obtains that Fe content is 30%, basicity is the Mn-rich slag of 2 simultaneously;
Step (5), the Mn-rich slag that step (4) is obtained and remaining high silicon manganese-silicon alloy stir wrap in carry out desiliconization, dephosphorization and increase manganese reacting, in alloy silicon content not higher than 10% time and stopped reaction;
Step (6), the alloy impouring that step (5) obtained are built with in the intermediate frequency furnace of aluminium scrap or aluminium ingot, and cold melt aluminium scrap or aluminium ingot under the covering of insulating covering agent, obtain manganese silumin, and the mass percent of its each component is as follows: Mn:76.8%; Si:8.5%; Al:6.02%; P:0.05%; C:0.04%; S:0.015%.
High-phosphorus manganese reserves used in the present embodiment are more, distributed more widely, price is relatively low, and the price that commodity manganese-silicon compared by the nonstandard high phosphorus manganese-silicon of its output is low by more than 20%.The present embodiment, by common coke, silica being added together with high-phosphorus manganese in mineral hot furnace, obtains superelevation phosphorus manganese-silicon and slag, this slag is carried out Water Quenching, can obtain cement raw material; In general high phosphorus manganese-silicon, the content of phosphorus is 0.6% ~ 1.2%, phosphorus content then belongs to very high content more than 0.6%, and carbon, phosphorus (C >=1.5% in the manganese-silicon obtained in the present embodiment, P >=0.6%) content all higher, the content height of carbon, phosphorus directly causes the easy efflorescence of manganese silumin, cannot be applied to smelting, therefore the direct object of this technique is exactly dephosphorization, carbon drop.Due to the element that phosphorus is very difficult removing, in order to achieve this end, first this technique selected to increase silicon, by manganese-silicon together with industrial silicon tankage, decarburization flux in intermediate frequency reaction in furnace, silicone content is promoted to 25% by 17%, and carbon content is down to less than 0.3% by more than 1.5%, after silicone content improves, extremely be conducive to removing phosphoric, then add silicocalcium or Si-Ba alloy, phosphorus content is down to less than 0.15% by 0.35%, then, by Australia ore deposit, lime and fluorite melt in electric arc furnace, obtain the Mn-rich slag that basicity is about 2, react with manganese-silicon again with this slag, phosphorus is removed further, simultaneously, also silicon is reduced, the content of carbon also increases Fe content, in the manganese-silicon now obtained, phosphorus content is 0.05%, silicone content is 8%, carbon content 0.04%, finally, carbon, the low-down manganese-silicon of phosphorus content again with aluminium scrap congruent melting, obtain manganese silumin, now in manganese silumin, the content of each component not only meets the requirement of smelting, and carbon, phosphorus content is very low, manganese silumin is made no longer to there is the problem of efflorescence.
The technique that the present embodiment adopts fundamentally changes and has innovated the technique thinking that manganese sial composite alloy is produced, make the poor assorted manganese ore being originally difficult to use in mn site doping is produced obtain rational application, also explore a practical way for the poor integrated application of assorted manganese ore of China and the upgrading of ferroalloy productor.
In addition, to issue on November 7th, 2012 and in " People's Republic of China's ferrous metallurgy industry standard YB/T4303-2012 " of formally implementing on March 1st, 2013, regulation has also been done to the content of element each in manganese silumin, as shown in table 1, known by table 1, the manganese silumin that the present embodiment obtains meets the requirement of the micro-carbon level of this standard completely.
Table 1 manganese silumin chemical composition YB/T4303-2012
Embodiment 2
A kind of high-phosphorus manganese described in the present embodiment produces pure manganese silumin technique, comprises the following steps:
Step (1), high-phosphorus manganese, coke, silica are dropped in mineral hot furnace, obtain liquid high phosphorus manganese-silicon, the mass percent of its each component is: Mn:69%; Si:16%; P:0.9%; C:1.9%; S:0.03%, all the other are Fe;
Step (2), get this liquid high phosphorus manganese-silicon 3000Kg in step (1), and will fill in the intermediate frequency furnace of industrial silicon tankage (siliceous 85%), decarburization flux and a small amount of insulating covering agent in its impouring, treat load melting complete, skim, come out of the stove, now in manganese-silicon, the mass percent of each component is Mn:57.5%; Si:28%; P:0.5%; C:0.15%; S:0.015%;
Step (3), the in-built silicocalcium of the manganese-silicon impouring (silicon: 55% will obtained in step (2), 28%) or Si-Ba alloy (silicon: 40% calcium:, barium: in the stirring bag of 25%) (note: be mass percent), a small amount of slag former, agitation as appropriate, now the high silicon manganese-silicon alloy phosphorus content of output is 0.12%;
Step (4), the high silicon manganese-silicon alloy that step (3) obtains is got 20%, impouring is equipped with in the electric arc furnace of Australia ore deposit, lime and fluorite, Australia ore deposit is mainly containing the Mn of about the 42% and Fe of about 8%, lime is then common lime raw material, containing the calcium oxide of about 85%, treat load melting completely can to come out of the stove, obtain micro-carbon ferromanganese, the mass percent of its each component is: Mn:81.5%; Si:0.7%; C:0.15%, also obtains that Fe content is 27%, basicity is the Mn-rich slag of 1.9 simultaneously;
Step (5), the Mn-rich slag that step (4) is obtained and remaining high silicon manganese-silicon alloy stir wrap in carry out desiliconization, dephosphorization and increase manganese reacting, in alloy silicon content not higher than 10% time and stopped reaction;
Step (6), the alloy impouring that step (5) obtained are built with in the intermediate frequency furnace of aluminium scrap or aluminium ingot, and cold melt aluminium scrap or aluminium ingot under the covering of insulating covering agent, obtain manganese silumin, and the mass percent of its each component is as follows: Mn:74.8%; Si:8.1%; Al:5.8%; P:0.045%; C:0.035%; S:0.018%.
Embodiment 3
A kind of high-phosphorus manganese described in the present embodiment produces pure manganese silumin technique, comprises the following steps:
Step (1), high-phosphorus manganese, coke, silica are dropped in mineral hot furnace, obtain liquid high phosphorus manganese-silicon, the mass percent of its each component is: Mn:65%; Si:17%; P:1.1%; C:1.6%; S:0.04%, all the other are Fe;
Step (2), get this liquid high phosphorus manganese-silicon 3000Kg in step (1), and will fill in the intermediate frequency furnace of industrial silicon tankage (siliceous 60%), decarburization flux and a small amount of insulating covering agent in its impouring, treat load melting complete, skim, come out of the stove, now in manganese-silicon, the mass percent of each component is Mn:60%; Si:27%; P:0.65%; C:0.35%; S:0.025%;
Step (3), the in-built silicocalcium of the manganese-silicon impouring (silicon: 55% will obtained in step (2), 28%) or Si-Ba alloy (silicon: 40% calcium:, barium: in the stirring bag of 25%) (note: be mass percent), a small amount of slag former, agitation as appropriate, now the high silicon manganese-silicon alloy phosphorus content of output is 0.19%;
Step (4), high silicon manganese-silicon alloy about 20% impouring step (3) obtained are equipped with in the electric arc furnace of Australia ore deposit, lime and fluorite, Australia ore deposit is mainly containing the Mn of about the 42% and Fe of about 8%, lime is then common lime raw material, containing the calcium oxide of about 85%, treat load melting completely can to come out of the stove, obtain micro-carbon ferromanganese, the mass percent of its each component is: Mn:78.5%; Si:0.9%; C:0.12%, also obtains that Fe content is 29%, basicity is the Mn-rich slag of 2.2 simultaneously;
Step (5), the Mn-rich slag that step (4) is obtained and remaining high silicon manganese-silicon alloy stir wrap in carry out desiliconization, dephosphorization and increase manganese reacting, in alloy silicon content not higher than 10% time and stopped reaction;
Step (6), the alloy impouring that step (5) obtained are built with in the intermediate frequency furnace of aluminium scrap or aluminium ingot, and cold melt aluminium scrap or aluminium ingot under the covering of insulating covering agent, obtain manganese silumin, and the mass percent of its each component is as follows: Mn:77.4%; Si:7.8%; Al:6.4%; P:0.045%; C:0.037%; S:0.014%.
Embodiment 4
A kind of high-phosphorus manganese described in the present embodiment produces pure manganese silumin technique, comprises the following steps:
Step (1), high-phosphorus manganese, coke, silica are dropped in mineral hot furnace, obtain liquid high phosphorus manganese-silicon, the mass percent of its each component is: Mn:71%; Si:18%; P:1.2%; C:2.0 %; S:0.04%, all the other are Fe;
Step (2), get this liquid high phosphorus manganese-silicon 3000Kg in step (1), and will fill in the intermediate frequency furnace of industrial silicon tankage (siliceous 68%), decarburization flux and a small amount of insulating covering agent in its impouring, treat load melting complete, skim, come out of the stove, now in manganese-silicon, the mass percent of each component is Mn:62.5%; Si:30.6%; P:0.7%; C:0.12%; S:0.027%;
Step (3), the in-built silicocalcium of the manganese-silicon impouring (silicon: 55% will obtained in step (2), 28%) or Si-Ba alloy (silicon: 40% calcium:, barium: in the stirring bag of 25%) (note: be mass percent), a small amount of slag former, agitation as appropriate, now the high silicon manganese-silicon alloy phosphorus content of output is 0.12%;
Step (4), the high silicon manganese-silicon alloy that step (3) obtains is got 20%, impouring is equipped with in the electric arc furnace of Australia ore deposit, lime and fluorite, Australia ore deposit is mainly containing the Mn of about the 42% and Fe of about 8%, lime is then common lime raw material, containing the calcium oxide of about 85%, treat load melting completely can to come out of the stove, obtain micro-carbon ferromanganese, the mass percent of its each component is: Mn:82%; Si:0.73%; C:0.06%, also obtains that Fe content is 29%, basicity is the Mn-rich slag of 2 simultaneously;
Step (5), the Mn-rich slag that step (4) is obtained and remaining high silicon manganese-silicon alloy stir wrap in carry out desiliconization, dephosphorization and increase manganese reacting, in alloy silicon content not higher than 10% time and stopped reaction;
Step (6), the alloy impouring that step (5) obtained are built with in the intermediate frequency furnace of aluminium scrap or aluminium ingot, and cold melt aluminium scrap or aluminium ingot under the covering of insulating covering agent, obtain manganese silumin, and the mass percent of its each component is as follows: Mn:76.2%; Si:8.1%; Al:6.2%; P:0.042%; C:0.033%; S:0.016%.
Embodiment 5
On the basis of the present embodiment any embodiment in embodiment 1 ~ embodiment 4, for improving the utilization ratio of manganese, accomplish effective utilization of resource, in step (5), Mn-rich slag and high silicon manganese-silicon alloy react except obtaining silicone content amount not higher than except the alloy of 10%, also obtain waste residue, carry out shrend when being controlled below 3% by the Fe content in waste residue, the slag after shrend is the very good material producing cement, has accomplished the recycling of waste material.
Embodiment 6
The high silicon manganese-silicon alloy that step (3) obtain, on the basis of embodiment 1, directly can be poured in mold, obtain high-Si aluminum cast product by the present embodiment.
In addition, also micro-carbon ferromanganese that step (4) obtain directly can be poured in mold, obtain micro-carbon ferromanganese product.
The present embodiment the different demands to product can adjust according to the difference of phosphorus content in manganese ore and user, obtain micro-carbon-manganese alloy, high silicon manganese-silicon alloy, manganese silicon aluminum alloy product, thus meet the different needs, simultaneously, raw material is changed into product as much as possible, achieves effective utilization of resource.
The above is only preferred embodiment of the present invention, and not do any pro forma restriction to the present invention, every any simple modification, equivalent variations done above embodiment according to technical spirit of the present invention, all falls within protection scope of the present invention.
Claims (5)
1. high-phosphorus manganese produces pure manganese silumin technique, it is characterized in that: comprise the following steps:
(1) high-phosphorus manganese, coke, silica are dropped in mineral hot furnace, obtain high phosphorus manganese-silicon, the mass percent of its each component is as follows: Mn:65 ~ 73%; Si:16 ~ 18%; P:0.6 ~ 1.2%; C:1.5 ~ 2.0%; S:0.03 ~ 0.04%, all the other are Fe;
(2) by filling in the high phosphorus manganese-silicon impouring obtained in step (1) in the intermediate frequency furnace of industrial silicon tankage, decarburization flux and a small amount of insulating covering agent, the silicon content of high phosphorus manganese-silicon being promoted to more than 25%, treating load melting complete, skim, come out of the stove;
(3) by the stirring bag of the in-built silicocalcium of high phosphorus manganese-silicon impouring that obtains in step (2) or Si-Ba alloy, a small amount of slag former, agitation as appropriate, obtains high silicon manganese-silicon alloy, and in the high silicon manganese-silicon alloy of now output, phosphorus content is not higher than 0.15%;
(4) high silicon manganese-silicon alloy obtained in step (3) is got 20%, impouring is equipped with in the electric arc furnace of Australia ore deposit, lime and fluorite, treat load melting completely can to come out of the stove, obtain carbon content not higher than 0.1% micro-carbon ferromanganese and Fe content be 25% ~ 30%, basicity is the Mn-rich slag of 1.8 ~ 2.2;
(5) Mn-rich slag step (4) obtained and remaining high silicon manganese-silicon alloy stir wrap in carry out desiliconization, dephosphorization and increase manganese reacting, in alloy silicon content not higher than 10% time and stopped reaction;
(6) be equipped with in the intermediate frequency furnace of aluminium scrap or aluminium ingot by the alloy impouring that step (5) obtains, cold melt aluminium scrap or aluminium ingot under the covering of insulating covering agent, obtain manganese silumin, and the mass percent of its each component is as follows:
Mn:70 ~ 80%; Si:5 ~ 10%; Al:4 ~ 10%; P<0.1%; C<0.1%; S:0.03 ~ 0.04%, all the other are Fe.
2. high-phosphorus manganese according to claim 1 produces pure manganese silumin technique, it is characterized in that: in described step (5), Mn-rich slag and high silicon manganese-silicon alloy react except obtaining silicone content not higher than except the alloy of 10%, also obtain waste residue, shrend is carried out to this waste residue, obtains the raw material that can be used for manufacturing cement.
3. high-phosphorus manganese according to claim 1 produces pure manganese silumin technique, it is characterized in that: the basicity of the Mn-rich slag that described step (4) obtains is 2.0 ~ 2.2.
4. high-phosphorus manganese according to claim 1 produces pure manganese silumin technique, it is characterized in that: the high silicon manganese-silicon alloy that described step (3) obtains can directly be poured in mold, obtains high-Si aluminum cast product.
5. high-phosphorus manganese according to claim 1 produces pure manganese silumin technique, it is characterized in that: micro-carbon ferromanganese that described step (4) obtains can directly be poured in mold, obtains micro-carbon ferromanganese product.
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